Development of Porous Ceramic-Immobilized Lipase Catalyst and Optically Active Fluorinated supramolecules

(1)低温固定化脂肪酶高效对映选择性催化体系的建立。(a)为了开发固定化脂肪酶，我们研究了涂覆在多孔陶瓷支架上的有机桥。有机桥通过共价键与多孔陶瓷结合。采用含异丁酸酯段的有机桥架用于脂肪酶催化外消旋醇的分离，在-30℃条件下固定化脂肪酶的对映选择性和催化活性均有显著提高。(b)为了进一步提高固定化脂肪酶的效率，我们对酰基化剂进行了优化。以丁酸乙烯酯为酰化剂，在-40℃时对映选择性和催化活性均达到最大。(2)光学活性氟化胺的研究进展及其在超分子材料中的应用。(a)通过脂肪酶催化的分离得到了含有五氟苯基的对映体纯氰丙烷。以手性氰丙烷为原料，合成了新型对映体纯的含五氟苯基和苯基的1,2-氨基醇。该化合物的x射线分析表明，五氟苯基与醇氧原子之间存在相互作用。这种相互作用为设计超分子材料提供了新的有用信息。(b)通过亚胺-蒎醇偶联反应合成了新型对映体纯的含五氟苯基的1,2-二胺。由于五氟苯基的强吸电子能力，与非氟衍生物相比，二胺的碱度降低。事实表明了五氟苯基对氮原子的影响。

(1) Development of highly effective and enantioselective catalysis system with immobilized lipase at very low temperatures.(a) For development of an immobilized lipase, we searched the organic bridges coated on porous ceramic support. The organic bridges were combined with porous ceramic by, covalent bonding. When the organic bridge containing isobutyric acid ester moiety was used for the lipase-catalyzed resolution of racemic alcohols, both of enantioselectivity and catalytic activity of the immobilized lipase were much enhanced at -30℃.(b) For further improvement of efficiency of the immobilized lipase, we optimized the acylating agents. When vinyl butanoate was used as the acylating agent, both of the enantioselectivity and the catalytic activity were maximized at -40℃.(2) Development of the optically active fluorinated amines and their application to supramolecular materials.(a) An enantiomerically pure cyanohydrine containing pentafluorophenyl group was obtained by using lipase-catalyzed, resolution. The novel enantiomerically pure 1,2-aminoalcohol containing pentafluorophenyl and phenyl group was synthesized from the chiral cyanohydrine. The X-ray analysis of the compound indicated existence of the interaction between pentafluorophenyl group and alcoholic oxygen atom. The interaction afforded new and useful informations for designing supramolecular materials.(b) The novel enantiomerically pure 1,2-diamine containing pentafluorophenyl groups was synthesized via imino-pinacol coupling reaction. The basicity of the diamine was reduced as compared with the non-fluorinated derivative due to the strong electron-withdrawing ability of the pentafluorophenyl groups. The facts showed the influence of the pentafluorophenyl groups for the nitrogen atom.